JP2566230B2 - Fluid processing method and processing apparatus - Google Patents

Abstract

A fluid treating apparatus (10) and method for treating fluid to remove undesirable constituents contained therein. The apparatus (10) and method include employing a bed of metal particulate matter (18). The metal particulate matter (18) is preferably chosen from metal having: favorable redox potentials relative to the redox potentials of the undesirable constituents so as to establish conditions for spontaneous oxidation and reduction reactions between the undesirable constituents and the metal particles (18) and/or having bacteriostatic or bactericidal properties in the case where the undesirable constituent sought to be treated is a bacteria.

Description

DETAILED DESCRIPTION OF THE INVENTION Background and Description of the Invention This application is a continuation application of US Patent No. 605,652, filed April 30, 1984.

The present invention relates generally to methods of treating fluids, and more particularly to devices and methods suitable for performing improved fluid treatments.
Industrial and domestic water supplies often contain undesirable components, which require treatment before use. Although the present invention is versatile, it has been recognized that it can be used in treating water to remove unwanted components contained therein, such as dissolved chlorine and bacterial components, or to inhibit growth.

In this context, industrial and utility processes often require large amounts of cooling water. Many water cooling operations utilize heat exchange for primary heat conditioning, resulting in an increase in the temperature of the cooling water passing through the device. This increase in temperature promotes the growth of organisms present in the water, resulting in a clogging of the system, for example, or a biological slime layer accumulating on the heat exchange surface, significantly reducing their efficiency. This causes the device to lose functionality.

Chlorination is the most common means of controlling bacteria in both cooling and drinking water systems. Although the biocidal properties of hypochlorous acid are effective in killing bacteria, hypochlorous acid itself can be detrimental to other equipment or processing systems used. In addition, excess chlorine in drinking water often imparts an undesirable taste and odor to water,
Runoff can be harmful to the environment. In this regard, EPAs have set limits on residual chlorine in effluents and must often employ dechlorination to remove excess residual chlorine produced by excess chlorination to comply with EPA guidelines.

Numerous systems have been proposed in the field of fluid treatment, especially in the field of commercial, industrial and domestic water treatment, some or all of which carry some undesirable characteristics, drawbacks or disadvantages. .

For example, ion exchange systems are commonly used to soften water and selectively remove certain impurities from water.
The effective medium of an ion exchange device is an ion exchange resin designed to remove unwanted constituents from the fluid and replace these undesirable constituents with less undesirable constituents. For example, a cation exchange resin used to remove elements such as calcium and magnesium that cause hardness is designed to give up the sodium (exchanged with calcium and magnesium) contained in the water that has passed through the ion exchanger at the same time. Will be done. Regardless of the particular ion exchange resin used, the resin bed will eventually be exhausted and the unit must be taken out of operation and regenerated to make it effective again. In addition to chemical depletion, iron bacteria can quickly fill the ion exchange resin tank and clog the chemical supply nozzle and other orifices. This resin is also susceptible to chemical degradation by the excess chlorine present, for example, during the bacterial treatment process. Therefore, the ion exchanger unit must be carefully maintained and monitored to ensure sustained acceptable performance.

Another common type of water treatment method is the reverse osmosis method. In this case, pressures above the osmotic pressure of the fluid are used to force the untreated water, usually at ambient temperature, into the selective membrane in a direction opposite that normally found in osmosis. Selective membranes are designed to be permeable to water but eliminate dissolved undesirable constituents. The success of this method largely depends on the development of suitable membranes. Membranes used in reverse osmosis generally suffer from stability problems with various temperatures, chemicals and pressures, as well as rate and capacity limitations. Just as bacteria can contaminate heat exchangers,
This can result in a contaminated film on the reverse osmosis membrane. When the water supply is treated with chlorine as an antibacterial agent, dissolved chlorine is highly effective in combating bacteria but often has a detrimental effect on reverse osmosis membranes. Furthermore, reverse osmosis devices must also be carefully assembled, maintained and monitored. Therefore, despite the complexity of the technology used, the end user is unable to maintain the system and perform the necessary sampling to ensure that the system is functioning according to the design specifications. , A failure may occur during processing.

Yet another common water treatment method is the use of activated carbon.
It is widely used for taste and odor control and for removing organic pollutants from water by adsorption. This is because activated carbon is characterized by having a high adsorptivity for gases, vapors, and colloidal solids. However, like the resin in an ion exchange device, the adsorption capacity of carbon will eventually be exhausted and the carbon must be regenerated or replaced. Therefore, systems employing activated carbon also need to be carefully monitored to determine media effectiveness. Another drawback of finished coal is that it collects microorganisms, including harmful bacteria, and provides a medium in which this kind of harmful bacteria can grow. As a result, the activated carbon that will purify the water can contaminate the water with harmful bacteria. In an attempt to overcome this drawback, manufacturers have attempted to obtain bacteriostatically active carbon by impregnating activated carbon with silver. But this kind of attempt was not entirely satisfactory. Achieves an effective bacteriostatic concentration of silver,
And it is difficult to stay within established EPA guidelines for dissolved silver content. Silver also has other drawbacks associated with its use. That is, the cost of silver itself can be an obstacle to economical water treatment.

The present invention provides a fluid treatment system and method that utilizes metal particulates to provide the undesirable characteristics of the prior art,
Overcoming the disadvantages and disadvantages, this material compares with the redox potential of the unwanted components to be treated,
It has a redox potential that favors the spontaneous redox reaction of the metal with unwanted components and / or is bacteriostatic or bactericidal if the unwanted component to be treated is a bacterium. The metal particulates can be of any desired shape, with various mesh sizes (preferably 4-400 mesh based on US standard screen sizes), which generally prevent particulates from escaping acid but at the same time the fluid is Flowing through it is arranged in a loose packed bed which is confined within the treatment vessel by means of permitting. Alternatively, a method in which these particles are adhered to each other to form an aggregated porous body in which the surface region is freely exposed can be adopted. Suitable methods for forming this type of agglomerated porosity include sintering methods, and the use of binders to cover all (or substantially all) surface area of the particles thereby contacting the fluid to be treated. A free exposure method is included for this purpose. An important embodiment of the present invention is directed to ice treatment equipment and water treatment processes that employ metal particulates (eg, zinc and copper, and mixtures and alloys thereof) to remove unwanted contaminants (eg, chlorine and bacteria). To do. An important aspect of the present invention in this connection is that the method is able to remove undesired pollutants of this kind economically and over a long period of time, which leads to weaknesses in most treatment systems, namely relatively With the finding that frequent system maintenance and monitoring are largely eliminated.

Another feature of the invention involves the use of a bed of metal particulates of this type in combination with other fluid treatment equipment such as activated carbon, reverse osmosis or ion exchange treatments. In this context, an important aspect of the present invention is that undesired elements and compounds that can be detrimental to the operation and life of other processes such as activated carbon, reverse osmosis and ion exchange, such as chlorine and bacteria. With the removal of.

Another feature of the present invention involves providing an apparatus and method of using a bed of metal particulates of this type with other types of fluid treatment equipment, such as activated carbon, ion exchange, or reverse osmosis. An important aspect of the invention in this connection involves the delay of the growth of bacteria on this kind of medium and / or the destruction of the bacteria which may be present on this kind of medium.

Another feature of the invention involves adjusting the pH of the fluid and then passing it through the bed of metal particulates described above. An important aspect of the invention in this context involves adjusting the pH of the fluid prior to treatment to enhance the removal of contaminants with pH-dependent redox activity.

Another feature of the invention includes a bed of metal granules of this type.
This involves using the individual containers in sequence with the pH feeder inserted between them. This fluid treatment method allows the user to utilize the pH of the feed fluid at the inlet of the first container to treat contaminants that are more responsive to treatment at the original feed fluid pH, and then at other pHs. The fluid can be treated again in the second vessel after the pH has been adjusted to treat contaminants that would be effectively treated.

Accordingly, an important object of the present invention is to provide an improved fluid treatment device and method.

Another object of the present invention is that it is economical to use, has a relatively long life, avoids frequent maintenance and monitoring, and eliminates the need to reclaim the processing medium, and thus other common processing methods, It is an object of the present invention to provide a fluid treatment device and method that obviates the need to dispose of concentrated pollutants inherent in reverse osmosis and ion exchange, for example.

Another object of the present invention is to provide a novel method for treating unwanted constituents present in fluids such as water, eg chlorine and bacteria, without such constituents being concentrated in the treatment medium. That is.

Another object of the present invention is the conditions under which a spontaneous redox reaction occurs between the metal particulates and the undesired components when the fluid contacts the metal particles relative to the redox potential of the undesired components to be treated. Is to provide a fluid treatment process that includes fluid treatment by passing a feed fluid containing undesired constituents to a bed of metal granules.

Another object of the invention is to first treat the fluid with undesired components present in conduction through the bed of metal granules, such as chlorine, which is generally detrimental to fluid treatment processes such as reverse osmosis or ion exchange. It is an object of the present invention to provide an improved fluid treatment method which brings this fluid into a general treatment process of this kind.

Another object of the present invention is to first pass the fluid through a conventional fluid treatment process, such as an activated carbon treatment process, and then pass the fluid through a bed of metal particles to treat unwanted components such as harmful bacteria. An apparatus and an improved method.

Another object of the present invention is an apparatus and apparatus for treating undesired components by passing a fluid through a bed containing both metal particulates and common treatment media such as activated carbon, ion exchange resins or reverse osmosis membranes. It is to provide an improved method.

These and other objects and advantages of the present invention include a fluid treatment apparatus that includes a bed of metal particulates, and a fluid treatment that includes passing a fluid containing undesirable elements and compounds to a bed of metal particulates of this type. Achieved by providing the law. The particulates are preferably selected from metals such as zinc and copper and mixtures and alloys thereof, which are undesired with the metallic particulates when the fluid is in contact with the metallic particles, in contrast to the unwanted constituents (eg chlorine) which one wishes to treat. It has a favorable redox potential in order to establish conditions under which spontaneous oxidation and reduction reactions occur with the sex component, and / or bacteriostatic or bactericidal properties when the unwanted constituent to be treated is a bacterium. Hold.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a vertical cross-sectional view of one form of the fluid treatment arrangement of the present invention showing a loosely packed bed of metal particulates.

FIG. 2 is a vertical cross-sectional view of one form of the fluid treatment apparatus of the present invention showing an activated carbon bed and a metal particulate bed that are separate from each other but are enclosed in a common housing.

FIG. 3 is a vertical cross-sectional view of one form of the fluid treatment apparatus of the present invention showing a continuous activated carbon bed and a metal granular material bed.

FIG. 4 is a vertical cross-sectional view of one form of the fluid treatment apparatus of the present invention showing a general treatment method using a bed of activated carbon or the like and a bed of metal particles contained in a common housing.

While an important aspect of the present invention is directed to the treatment of water, especially drinking water, it is understood that the apparatus and method of the present invention can be advantageously employed in the treatment of a variety of other feed fluids containing a variety of undesirable contaminants. Will be recognized. Thus, for purposes of explanation only, the present invention will be described in large part in the form where water is the feed fluid to be treated.

Modifying the composition of a particular water supply for the particular pollutants contained therein, such as dissolved chlorine and nitrates, by contacting this water with metals such as aluminum, iron, zinc, tin and copper, and mixtures and alloys thereof. This time it was possible to find out. For example, passing water containing a high concentration of dissolved chlorine through a canister containing metal particulates (eg brass) was found to significantly reduce the chlorine levels detected in the effluent, if not eliminated. Was given.

It has also been found that this fluid treatment method is also effective in significantly reducing and / or removing the nitrate concentration of effluent under certain conditions. Furthermore, treatment media containing brass granules are used for common bacterial pollutants such as E. coli and Pseudomonas.
It has been found to act as an effective fungicide and / or bacteriostat for s). When water containing dissolved iron, which may contaminate clothes when contacted, such as iron (II), is conducted to the brass floor, the effluent does not apparently contain dissolved iron, and even if it comes in contact with it, clothes Was found not to pollute. Furthermore, it was found that when water contaminated with tannin was passed through a brass bed, the effluent was transparent and apparently contained no tannin. As a result of these findings, it is believed that those developed in accordance with the present invention find widespread use in other types of inorganic impurities such as hydrogen sulfide and sulfur dioxide (to name only a few), and organic pollutants. .

Moreover, under normal operating conditions, the useful life of this type of fluid treatment method is believed to be far beyond that of other conventional treatment systems. This finding is thus useful in eliminating one of the main drawbacks of the general system, namely the need to frequently replenish the available processing sources, and at the same time the system to be regularly maintained and monitored. Brings considerable progress in the technical field.

Moreover, this method has wide potential utility for various home, commercial and industrial applications. Keeping in mind, for example, that chlorine and iodine are effective antimicrobial agents,
Drinking water (especially in foreign land) is treated in a safe form that is more palatable by first treating the water by chlorination or iodine treatment and then contacting the chlorinated or iodine treated water with metal particles according to the present invention. Could be changed to

As mentioned above, this development is intended to apply to other fluid media besides water treatment, including other liquid and gaseous fluid media themselves and gaseous fluid media dissolved in liquids. . For example, the removal of harmful gases, especially halogens such as chlorine, bromine and fluorine, by passing them through a canister containing a bed of metallic material is contemplated by and within the scope of the present invention. This type of application provides an alternative to polluted air purification, for example in gas masks, or can be used as an alternative to the more general scrubbing method or in combination therewith.

Referring now to the drawings, FIG. 1 illustrates the present invention typically embodied in an apparatus for treating a fluid (such as water), generally designated as 10, which apparatus has an inlet 12, an outlet 1
4, and a treatment tank 16 containing a packed bed of metal particulates 18 is shown. The treatment tank 16 may be of various shapes and sizes depending on the intended use. For example, processing tank
16 may take the form of a canister shown in FIG.

As shown in FIG. 1, the fluid treatment tank 16 has an impermeable side wall.
20 and top and bottom walls 22 and 24. Upper wall
22 and the bottom wall 24 are each provided with a treatment tank 16 for treating the treated fluid.
An inlet 12 and an outlet 14 are included for entering and exiting. Fluid treatment tank 16 further includes perforated or permeable top plates 26 and 28. Each of these introduces a fluid into the fluid treatment tank 16 and then discharges it while the metal particulates 18
Prevent them from escaping. According to another aspect of the invention,
The bed of metal particles can be used in combination with or in connection with other fluid treatment media to provide an enhanced fluid treatment system.

2-4 show examples of such enhanced fluid treatment systems. In FIG. 2, apparatus 40 includes fluid treatment vessel 16, which further includes a perforated or permeable midplate 42,
This divides the tank 16 into an upper chamber 44 and a lower chamber 46. The upper chamber contains a conventional fluid treatment medium, such as activated carbon 48, and the lower chamber contains a packed bed of metal particulates 18. In the case of FIG. 4, the apparatus 50 includes a treatment vessel 16 containing a conventional fluid treatment medium, eg activated carbon 48, admixed with the metal particulates 18. The treatment medium 48 can, of course, be any conventional treatment medium, another example being a reverse osmosis medium, in which the fine mesh metal particulates 18 are flocked onto the membrane. be able to.

In FIG. 3, device 60 includes two fluid treatment vessels 62 and 16 connected in series. The fluid treatment tank 62 includes an inlet 64 and an outlet 66, which are connected to the inlet 12 of the fluid treatment tank 16. The fluid treatment tank 62 contains a packed bed of conventional treatment media, such as activated carbon 66. Fluid treatment tank 62 is an impermeable side wall
68, and top and bottom walls 70 and 72. Upper wall
70 and the bottom wall 72 respectively contain a treatment tank for the fluid to be treated.
An inlet 64 and an outlet 66 are included that enter and exit 62. The fluid treatment tank 62 further includes perforated or permeable top and bottom plates 74 and 76, which respectively introduce fluid into the treatment tank 62 and discharge it from the activated carbon.
Prevent the escape of 66.

It will be appreciated that the relative positions of the above fluid treatment media shown in FIGS. 2 and 3 may be reversed depending on the intended application. For example, if the common treatment medium is activated carbon as described above, it may be desirable to place a bed of metal particulates downstream of the activated carbon to treat harmful bacteria contained in the fluid discharged from the activated carbon. . On the other hand, if the typical treatment medium is a reverse osmosis medium or an ion exchange medium, place a bed of metal particulates upstream of this type of medium to remove components such as dissolved chlorine that may be harmful to these mediums. It would be desirable to remove.

The present invention also contemplates the use of several different metals and their mixtures and alloys. Although the present invention is not limited to any particular theory, the process of the present invention is not limited to spontaneous oxidation-at least with respect to inorganic components, such as dissolved chlorine.
It is assumed to be achieved by a reduction reaction. Thus, the metal particulates are relatively good redox agents as opposed to the unwanted components that one wants to treat, which allows the spontaneous interaction between the metal particulates and the unwanted components when the fluid contacts the metal particulates. It is believed that it should be selected from the group of metals, including their mixtures and alloys, where the conditions for the typical oxidation and reduction reactions are established.

The relative susceptibility to reduction or oxidation of different species is
It can be predicted from their standard reduction potential (E ° value at 25 ° C). By comparing the E ° values for different species, one can determine whether redox occurs spontaneously. According to the invention, a metal which is a relatively good redox agent compared to the element or compound to be treated is a metal which is expected to react spontaneously with this type of element and compound.

For example, chlorine dissolved in water at 25 ° C with a pH of about 7 is HO
Cl and ClO ^- exist as, in the acidic side, HOCl is dominant, the base side ClO ^- predominates. ClO For the sake of simplicity ^-
Assuming that is the reactive species, the following redox reactions are representative of those contemplated by the present invention.

Zn (s) → Zn ²⁺ (aq) + 2e ⁻ E ° = 0.76V ClO ⁻ (aq) + H ₂ O + 2e ⁻ → Cl ⁻ (aq) + 2OH ⁻ (aq) E ° = 0.89V Zn (s) + ClO ⁻ ( _{aq) + H 2 O → Zn} 2+ + Cl - (aq) + 2OH - (aq) E = 1.65V Cu (s) → Cu 2+ (aq) + 2e - E ° ^{= -0.34V ClO - (aq) +} H 2 O + 2e ^{- → Cl - (aq) +} 2OH - (aq) E ° = 0.89V Cu (s) + ClO - (aq) + H 2 O → Cu +2 (aq) + Cl - + 2OH - E = + as 0.55V are calculated zinc and copper are both hypochlorite (ClO ^-) and react spontaneously respectively, theoretically because towards zinc has a greater positive potential will become more spontaneous.

Since zinc and copper are both relatively good reducing agents for common inorganic pollutants, such as chlorine, and both are tolerated in solution at moderate concentrations without adverse effects, It is the preferred metal. Other metals, such as iron and aluminum, are also theoretically good reducing agents, but these metals have drawbacks which limit their use in general commercial applications. For example, iron having a relatively high concentration is tolerated in drinking water without poisoning, but such a concentration easily supplies iron bacteria and, when used for household purposes, easily contaminates articles such as clothes. In this regard, when water containing dissolved iron, which may contaminate clothing when contacted, such as iron (II), is passed through the brass floor, the dissolved water apparently contains no dissolved iron, It has now been found that contact with it does not contaminate clothing. Furthermore, iron-based metal particle beds are prone to premature clogging. Also, aluminum-based treated floors are more susceptible to scavenging (Sca
b), that is, it is prone to oxide coatings on the surface and is therefore practically ineffective after short periods of use.

In practice zinc and copper alloys, such as brass,
It has been found to be more effective at removing dissolved chlorine than pure zinc or pure copper or heterogeneous mixtures thereof. In addition to the noted effectiveness of brass, brass is also a preferred metal from a chemical safety standpoint. This is especially so in aqueous media. This is because brass does not have a vigorous reactivity to aqueous fluids as shown by metals such as pure sodium, potassium, calcium or zinc.

Copper / zinc alloys, such as brass, are the preferred metals from the standpoint of metal concentration dissolved in the effluent. In this connection, it is noted that the by-products of the redox reaction of zinc, copper and their alloys with inorganic pollutants, such as dissolved chlorine, are dissolved zinc, dissolved copper, and mixtures thereof, respectively. EPA, albeit relatively dilute, when treating drinking water that has been over-chlorinated with zinc or copper alone.
Dissolved metal concentrations may exceed the guidelines recommended by. As will be discussed further below, copper / zinc alloys, such as brass, can be effectively removed by removing undesired metal concentrations by more conventional processing methods such as ion exchange or reverse osmosis. It was found that the resulting dissolved metal concentrations when used as are well within the current EPA guidelines for dissolved zinc and dissolved copper in drinking water.

As mentioned above, another aspect of the invention is a purification process by passing water through a bed of metal particulates (eg brass) and common treatment methods such as reverse osmosis or ion exchange or activated carbon. Semi-permeable membranes often used in reverse osmosis processes, such as cellulose acetate, are particularly advantageous due to the fact that they are often subject to decomposition by dissolved chlorine, as are divinylbenzenes often used to crosslink ion exchange resins. . By using a brass bed in conjunction with a reverse osmosis membrane or ion exchange device, the life of the membrane or resin can be substantially extended. Furthermore, common treatment methods using reverse osmosis, ion exchange and activated carbon, respectively, are susceptible to bacterial contamination and / or bacterial accumulation, respectively. In this regard, copper or copper alloys, such as brass, are used in the treatment system to combat E. coli and other unwanted organisms commonly found in sewage-contaminated water supplies, and bacteria such as Pseudomonas spp. Was found to be effective.

The term "brass" is used herein to refer to copper-zinc alloys in general, and alloys of this type may contain other components and / or are commonly referred to by different nomenclature. It will be appreciated. Alloys commonly referred to as bronze containing, for example, copper and zinc, including (but not limited to)
Art bronze composed of 57% Cu-40% Zn-3% Pb,
Almost 58.5% Cu-39% Zn-1.4% Fe-1% Sn-0.1% M
Manganese bronze A composed of n, and approximately 65.5% Cu
-23.3% Zn-4.5% Al-3.7% Mn-3% Manganese bronze B composed of Fe, as well as other metals, such as 60%
The Munz metal composed of Cu-40% Zn, commonly referred to herein as brass, is within the scope of the invention.

If the metal of choice is brass, contaminants such as iron filings and other foreign matter (brass activity can be impaired from the brass surface by washing the brass with, for example, a hydrochloric acid solution and then rinsing the brass. ) Will be washed away. However, it has been recognized that brass surfaces exposed to the atmosphere or feed fluids (eg, water) can cause green rust. It appears to be a carbonate and / or oxide complex. When the surface itself is physically scraped to remove the green rust, the removed rust also exhibits an excellent purification action.

A qualitative analysis of water treated by adding chlorine and passing it through a brass bed showed that this type of treatment consistently reduced the amount of chlorine in the water. Examples I and II set forth below describe the qualitative analysis of the composition both before and after treatment in separate laboratories for the brass used for water treatment and the treated water, respectively. As described in Example I below, analysis of the brass showed that the brass composition actually changed as would be expected if the oxidation-reduction process occurred by passing water through the brass bed. Was done. Also, as shown in Example II below, a separate laboratory analysis of the influent and the effluent that passed through the brass bed showed that chlorine contained in the influent was substantially removed. confirmed.

EXAMPLE I 7.6 cm x 15.2 cm (3 in x x 14 x 30 mesh brass trapped between screens to prevent brass escape.
Water was passed through the cylinder containing the 6 inch) packed bed. The water conducted to the brass bed was obtained from the Village of Constantine Water Station, Michigan and is not chlorinated but contains about 10-13 ppm dissolved nitrate. Chlorine was introduced into the influent in an amount of about 2 to 13 ppm to examine the extent of the decrease in chlorine level. After approximately 193 m ³ (51,000 gallons) of water has passed through the brass floor, the brass floor is approximately 1.3 m (1/2
Inch) reduced. A fresh brass sample that made up the brass floor,
And brass samples taken from the brass bed after passage of approximately 193 m ³ (51,000 gallons) of water were analyzed.

The elemental composition of these samples was measured by direct coupling plasma atomic emission spectrometry using a Beckman Spectraspan VI spectrometer. 0.1000g in 50/50 concentrated nitric acid /
A sample for plasma emission analysis was prepared by dissolving in 20 ml of a mixture of distilled water. The total solution weight was then brought to 100.00 g by adding distilled water.

The elemental composition was measured as the average of the values obtained from the following emission series for each element. Copper: 213.598 nm., 233.008 nm; Iron: 2
38.204nm., 259.940nm., 371.994nm .; Zinc: 213.856nm., 20
6.200nm., 202.548nm .; Lead: 104.783nm., 283.306nm, .368.3
48nm .. The results were as follows. Analytical treatment of brass Copper after pretreatment Copper% 59.2 65.0 Zinc% 35.2 27.8 Lead% 2.5 2.5 Iron% 0.2 0.2 The emission wavelengths of tin and aluminum were also examined, but these elements could not be detected at a 1: 1000 sample dilution. It was

Example II Influent water and the brass floor of Example I at about 193 m ³ (51,000
Gallons of water were used to treat and then two sets of samples of effluent were passed to separate laboratories for analysis. Sample set A was non-chlorinated tap water supplied by the Village of Constantine Water Station in Michigan, and sample set B was tap water with chlorine added. The results of each analysis are as follows. Sample set A Parameter unit Inflow Outflow Nitrit nitrogen Nitrogen mg / 10.35 9.34 Nitrate + Nitrit mg / 0.01 0.01 Organic nitrogen mg / 10.35 9.35 Aluminum (Al) mg / 0.5 0.5 Copper (Cu) mg / 0.04 0.27 Iron (Fe) mg / 0.05 0.34 Potassium (K) mg / 1.00 1.47 Sodium (Na) mg / 3.8 5.2 Zinc (Zn) mg / 0.12 1.3 Sample Set B Parameter Unit Inlet Outflow Chloride mg / 29.5 32.0 Chlorine mg / 13.0 0.1 Nitrate Nitrogen mg / 11.35 10.69 Nitrite nitrogen mg / 0.01 0.01 Nitrate + nitrite mg / 11.35 10.69 Aluminum (Al) mg / 0.5 0.5 Calcium (Ca) mg / 93.0 94 Copper (Cu) mg / 0.05 0.26 Magnesium (Mg) mg / 24.0 24.4 Potassium (K) mg / 1.02 1.06 Sodium (Na) mg / 17.1 17.8 Zinc (Zn) mg / 0.11 4.5 Each of the above examples is presented to explain the method of the present invention and the effects obtained thereby, and its general range To limit It's not meant to be. As best shown by the results of Sample Set B of Example II, the method of the present invention is effective in removing undesired contaminants such as dissolved chlorine. The concentration of cations, such as zinc and copper cations, actually increased in the effluent water as would be expected if it occurred during the oxidation-reduction process.

Furthermore, it was found that inflowing tap water with a pH of about 6.9 had a pH of about 7.2 after passing through the brass bed. It is further noted that the pH value of water, especially water with acidic pH values, increased as a result of passing through the brass-treated bed. This is a particularly advantageous feature of the present invention because chloride ions are generally present in drinking water, and chloride is an ion generated after brass treatment when chlorine is the target contaminant.
Chloride ions are potentially corrosive substances in acidic media. By increasing the pH of the treated water at the same time as the treatment, the potential corrosive action of chloride ions present tends to be neutralized.

This treatment also reduced the level of dissolved nitrate in the water, as shown by the results for both sample sets A and B of Example II. It has been observed that when the fluid is at least slightly acidic, for example having a pH of 6.5 or less, the process of the present invention promotes conversion of dissolved nitrate and significantly reduces dissolved nitrate concentration. It was found that the conversion of dissolved nitrate in acidic medium is reversible to some extent, that is, the presence of dissolved nitrate can be detected by subsequently increasing the pH value of the effluent. In this connection, it was surprisingly found that at relatively high pH values, for example pH values between 10 and 12, nitrate removal can be effected effectively and apparently irreversibly.

Thus, conventional acid feeders can be incorporated into the water treatment process provided that the unwanted components are more effectively removed in the acidic medium. Alternatively, if the undesired components are more effectively removed in the basic medium, pretreatment with a general base feeding device can be adopted. When treating multiple elements or compounds that require different pH, a continuous bed of metal granules (eg brass) is placed in sequence with a common suitable acid or base feeder inserted between them. The water to be treated can be conducted.

Furthermore, it was found that the rate and extent of contaminant removal depended on the metal-fluid contact time. Thus, increasing the contact surface area of the packed bed, for example by using a smaller mesh metal, will increase the rate and extent of removal. Alternatively or in conjunction therewith, the fluid flow rate may be reduced to provide a longer contact period.
Further, it has been found that supplying oxygen to the fluid or metal particulates can enhance the process by, for example, injecting air into the fluid or exposing the bed of metal particulates to the atmosphere.

The mesh size of the metal particles can be changed appropriately,
It was also found that this also had an effect on the treatment of the fluid. For example, a typical mesh size for metal particulates would be 4-400 mesh based on US standard screen sizes. Both mesh sizes above and below this range can be employed, but a mesh size of 4-30 mesh will usually be preferred for most applications. It will be appreciated that the metal particulates may be provided in other alternative forms, for example in the form of agglomerated porous bodies made by adhering these particulates into a desired shaped porous body. Suitable methods for producing this type of agglomerated porosity include the use of sintering methods and binders whereby all, or substantially all, of the surface area of the particles and the fluid being treated therewith. Includes a method of leaving it freely exposed for contact with.

It has been found that brass composed of various weight percent copper and zinc gives different effluent concentrations of dissolved metals. In this regard, and in relation to current emission regulations,
Brass with a copper: zinc ratio of about 1: 1 is preferred, brass with a copper: zinc ratio of about 3: 2 is more preferred, and brass with a copper: zinc ratio of about 7: 3 is highly preferred. It is, of course, recognized that copper is a better bactericidal and bacteriostatic agent than zinc, thus increasing the% copper in brass results in an enhanced bacteriostatic / bacteriostatic treatment. Let's do it.

A 51 cm (60 inch) packed bed of 14 x 30 mesh brass housed in a cylinder with a diameter of 15.2 cm (6 inches) provides the user's total pressurized water flow at home, without the need to replace the brass bed over the years. , It is considered that chlorinated influent water is effectively treated.

Examples III and IV below show separate studies of water inoculated with Escherichia coli and Pseudomonas, respectively; brass; 50% brass and 50% activated carbon mixture respectively; zinc; copper; and before and after treatment with activated carbon. 3 shows a quantitative analysis performed by the laboratory.

Example III Escherichia coli for initial inoculation was prepared from standard overnight cultures grown on standard agar and suspended in phosphate buffered saline. Single strength tryptic soy broth medium was added to the inoculum suspension to give a final tryptic soy broth medium concentration of 10%, thus obtaining the appropriate utilization nutrients for growing bacteria.

About 100 cm ³ of each of the following test materials was placed in each 400 ml beaker.

Test material 1. Brass shavings (rough elemental composition: 70% Cu and 30% Z
n (weight)); 2. 50:50 mixture of brass (same as above) and commercial activated carbon particles; 3. Granular zinc; 4. Granular copper; 5. Commercial activated carbon.

The inoculum (prepared as described above) was added to each beaker in an amount sufficient to bring the liquid level just below the surface of the test material. The inoculum was counted for microbes prior to addition of test material. Incubate each beaker for 16 hours at room temperature, then 1 ml of the resulting fluid
The microorganisms were counted.

 The results were as follows.

Tests with brass, 50% brass / 50% activated carbon, zinc and copper were performed on the same day with the same inoculum. The test with activated charcoal was also carried out later in a separate laboratory with different inoculum prepared in the same manner as above.

Example IV Pseudomonas spp. For initial inoculation was prepared from overnight stock cultures grown on standard method agar and suspended in phosphate buffered saline. Add a single strength tryptic soybean broth medium to the inoculation suspension,
A final tryptic soy broth medium concentration of 10% was obtained, thus obtaining suitable utilization nutrients for growing bacteria.

About 100 cm ³ of each of the following test materials was placed in each 400 ml beaker.

Test material 1. Brass shavings (rough elemental composition: 70% Cu and 30% Z
n (weight)); 2. 50:50 mixture of brass (same as above) and commercial activated carbon particles; 3. Granular zinc; 4. Granular copper; 5. Commercial activated carbon inoculum (prepared above) in each beaker Was added in an amount sufficient to bring the liquid surface directly below the surface of the test material. The inoculum was counted for microbes prior to addition of test material. Incubate each beaker for 16 hours at room temperature, then 1 ml of the resulting fluid
The microorganisms were counted.

 The results were as follows.

The above examples are presented for explaining the method of the present invention and the effects obtained thereby, and are not intended to limit the general scope thereof. As mentioned above, both copper and brass proved to be extremely effective bactericides when used alone as treatment media. Example III
As shown best in, activated carbon provided a breeding ground for bacterial growth, and a 100-fold or more increase in bacterial was observed when activated carbon was used alone. However, an effective bactericidal medium was obtained by mixing brass shavings with activated carbon.
Of course, it will be appreciated that copper or brass can be used in combination with other fluid treatment methods, such as ion exchange and reverse osmosis to provide similar bactericidal / bacteriostatic media. further,
It will be appreciated that the metal-based bactericide may be separate from the other treatment medium or may be integrated therewith, for example by impregnating activated carbon with copper or brass. Example IV shows that the present invention is also effective in suppressing the growth of organisms having relatively large resistance to antimicrobial agents, such as Pseudomonas sp.

In addition to chemically treating undesired components, the method of the present invention is utilized to physically pass undesired suspended solids. The invention of this aspect is particularly utilized to remove suspended iron. This iron is naturally present in water, as a result of pretreatment such as chlorination, or as a result of reaction with the bed of metal particles used in the method. If the water is pretreated with chlorine for the treatment of dissolved iron, the method will not only pass through the resulting suspended iron, but will also treat the chlorine remaining in the water. The canister containing the metal particulate bed can be backwashed periodically to remove excess material collected in the particulate bed and to clear the particulate bed from clogging.
However, unlike other processing methods, such as reverse osmosis and ion exchange, this type of backwash does not remove concentrated unwanted components.

Another aspect of the invention is to conduct water through both the metal particulate (eg brass) bed and the wood and / or super-auxiliary (eg sand) bed to enhance the undesired suspension. This is a purification method.

One of ordinary skill in the art will recognize that many modifications and variations can be made without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be limited only by the claims.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C02F 1/50 531 C02F 1/50 531F 540 540D 550 550B 550H 560 560B 560D 560E 1/58 ZAB 1 / 58 ZABA 1/64 CCZ 1/64 CCZZ 1/66 510 1/66 510A 521 521J 530 530B 540 540A 540G (56) Reference JP 61-502103 (JP, A) JP 60-147283 (JP, 147283) A) JP 55-64898 (JP, A) JP 61-178089 (JP, A) JP 61-72099 (JP, A) JP 56-111081 (JP, A) -106697 (JP, U) Actual public Sho 54-45020 (JP, Y2)

Claims (25)

(57) [Claims] 1. A method of treating a fluid to kill and control unwanted bacterial constituents contained in the fluid, the fluid containing said constituent comprising at least 50% by weight copper. / A method of killing and inhibiting said components by contacting them with a fine metal of a zinc alloy. 2. The method according to claim 1, wherein the contacting is carried out by passing a fluid through a bed of fine metal of a copper / zinc alloy. 3. The method according to claim 1 or 2, wherein the fine metal is a metal particle. 4. The method of claim 1 wherein the ratio of copper to zinc in the alloy is 1: 1 by weight. 5. A method according to claim 1 wherein the ratio of copper to zinc in the alloy is 3: 2 by weight. 6. The method of claim 1 wherein the ratio of copper to zinc in the alloy is 7: 3 by weight. 7. An improved activated carbon type fluid treatment medium, characterized in that it comprises finely divided metals of copper and zinc intimately mixed with activated carbon. 8. The activated carbon type fluid medium according to claim 7, wherein the fine metal is metal particles. 9. Copper and zinc are present in the form of a copper / zinc alloy,
The activated carbon type fluid treatment medium according to claim 7. 10. The copper content in the copper / zinc alloy is at least 50.
The activated carbon-type fluid treatment medium according to claim 9, which is in a weight percentage. 11. A device for treating a fluid, said device comprising means for connecting the device to a supply part of a fluid to be treated; a first fluid treatment medium comprising fine metal of copper and zinc and activated carbon. A second fluid treatment medium containing a chamber means; and a combination of a fluid inlet passage and a fluid outlet passage communicating with the chamber means; and the chamber means allowing the fluid to flow through the treatment medium and the treatment medium. The fluid treatment arrangement configured and arranged to prevent escape of the fluid. 12. The fluid treatment apparatus according to claim 11, wherein the fine metal is metal particles. 13. The fluid treatment arrangement of claim 11 wherein copper and zinc are present in the form of a copper / zinc alloy. 14. A copper / zinc alloy having a copper content of at least 50.
14. The fluid treatment device of claim 13, which is in weight percent. 15. A device for treating a fluid, said device comprising means for connecting the device to a supply of the fluid to be treated; a first fluid treatment medium consisting of fine metal of copper and zinc and ions. A chamber means enclosing a second fluid treatment medium that is an exchange resin treatment medium; and a combination of a fluid inlet passage and a fluid outlet passage in communication with the chamber means; and the chamber means allowing fluid to flow through the treatment medium. And configured and arranged to prevent escape of the processing medium,
The fluid treatment device. 16. The fluid treatment apparatus according to claim 15, wherein the fine metal is metal particles. 17. The fluid treatment arrangement of claim 15 wherein copper and zinc are present in the form of a copper / zinc alloy. 18. The copper content of the copper / zinc alloy is at least 50.
18. The fluid treatment device of claim 17, wherein the fluid treatment device is in weight percent. 19. A device for treating a fluid, said device comprising means for connecting the device to a supply of the fluid to be treated; a first fluid treatment medium consisting of finely divided metal of copper and zinc and a reverse. Chamber means for enclosing a second fluid treatment medium which is an osmotic treatment medium; and a combination of fluid inlet passages and fluid outlet passages communicating with the chamber means; and the chamber means allowing fluid to flow through the treatment medium. And the fluid treatment arrangement configured and arranged to prevent escape of the treatment medium. 20. The fluid treatment apparatus according to claim 19, wherein the fine metal is metal particles. 21. The fluid treatment arrangement of claim 19 wherein copper and zinc are present in the form of a copper / zinc alloy. 22. The copper content in the copper / zinc alloy is at least 50.
The fluid treatment device of claim 21, wherein the fluid treatment device is in weight percent. 23. A fluid treatment method for removing suspended tannins contained therein, comprising removing the tannins by contacting the fluid containing the tannins with a fine metal of a copper / zinc alloy. Consisting of the above method. 24. A fluid treatment method for increasing the pH of a fluid, said method comprising contacting said fluid with a fine metal of a copper / zinc alloy. 25. A fluid treatment method for removing contained dissolved iron, which comprises removing the dissolved iron by contacting the fluid containing the dissolved iron with a fine metal of a copper / zinc alloy. Consisting of the above method.